CN103201256A - Process for preparing esteramide compounds - Google Patents
Process for preparing esteramide compounds Download PDFInfo
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- CN103201256A CN103201256A CN2011800317745A CN201180031774A CN103201256A CN 103201256 A CN103201256 A CN 103201256A CN 2011800317745 A CN2011800317745 A CN 2011800317745A CN 201180031774 A CN201180031774 A CN 201180031774A CN 103201256 A CN103201256 A CN 103201256A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Abstract
The present invention relates to a process for preparing esteramide compounds. More particularly, the invention relates to a process for preparing esteramide compounds by reaction between a diester and an amine, in the presence of a basic compound, in which - the amine is solubilized in an organic solvent or in the diester, - when the amine is solubilized in an organic solvent, the diester is added to the reaction mixture comprising the amine and the basic compound, - when the amine is solubilized in the diester, the basic compound is added to the reaction mixture comprising the amine and the diester (II), - the reaction is carried out at a temperature greater than or equal to 30 DEG C, - the amine is present in a molar excess ranging from 0.01 to 50%, relative to the diester.
Description
Technical field
The present invention relates to a kind of method for the preparation of the carboxylic acid amide esters compound.
More specifically, the present invention relates to a kind of method for preparing the carboxylic acid amide esters compound by the reaction between diester and the amine.
Background technology
The carboxylic acid amide esters compound is well-known as the application of solvent because of them, particularly is used as solvent in plant protection is used, described in document WO 2009/092795 for example.
Existing several for the approach that obtains described carboxylic acid amide esters compound.
The pyroreaction that document US 4588833 is described a kind of unsaturated amides by cobalt catalysis and pure and mild carbon monoxide prepares the method for carboxylic acid amide esters.
Document US 3417114 has been described a kind of while preparation formula in embodiment 9 be MeOOC-(CH
2)
3-CONMe
2Carboxylic acid amide esters compound (DMGME) and formula be Me
2NOC-(CH
2)
3-CONMe
2The method of diamide compound (TMG), separate this two kinds of compounds by distillation subsequently.In order to carry out this reaction, the gaseous state dimethylamine blasted in the medium that comprises dimethylated pentanedioic acid that purifying is in advance crossed and sodium methoxide solution two hours.Then two kinds of compounds (DMGE and TMG) from the complex mixture that obtains by distilling separated opening.
Document US 3288794 has been described the method identical with document US 3417114, and prepares N simultaneously with the similar operation process, N-dimethyl hexanamide methyl esters and N, and N, N ', N '-tetramethyl-adipamide also separates by distilling subsequently.
Under the situation of diester, the method for above-mentioned prior art does not have selectivity to carboxylic acid amide esters.And the normally main ratio of the ratio of diamide and carboxylic acid amide esters are considered to fail the fully by product of reaction.
In addition, for these methods, need the step for the purifying diester before reaction, this makes method complicated.
After reaction, such method also needs the processing of difficult control and expensive reaction medium to separate diamide and carboxylic acid amide esters, for example is example by distillation.
And for these methods of prior art, the crude product of formation may have the strong safran color that is unfavorable for follow-up use.Therefore product carries out extra purification step.All these purification process make the method for producing carboxylic acid amide esters complicated.
In order to attempt overcoming optionally problem of low carboxylic acid amide esters, operate at low temperatures by the cooling reaction medium usually, namely be lower than under the room temperature.Yet, reduce the kinetics that temperature of reaction reduces reaction significantly, and therefore reduce the productivity of this method significantly.
Therefore, need find a kind of method of carboxylic acid amide esters selectively being produced carboxylic acid amide esters by diester.And this method should be used in industrial equipments easily.Another requirement that must satisfy of this method is that the kinetics of reaction must be big.At last, should should be efficiently for the production of the method for carboxylic acid amide esters.
Summary of the invention
For this reason, the present invention proposes a kind of method of the carboxylic acid amide esters compound for the preparation of following formula (I):
R
1OOC-A-CONR
2R
3(I)
Be included in the step that the amine of the diester compound that makes following formula (II) under the existence of basic cpd and following formula (III) reacts:
R
1OOC-A-COOR
1(II)
HNR
2R
3(III)
Wherein:
A is covalent linkage, or comprises the divalent alkyl of the straight or branched of 1～12 carbonatoms,
R
1Be the substituted alkyl alternatively that comprises 1～36 carbon atom,
R
2And R
3Identical or different, for being selected from hydrogen atom and comprising group in the substituted alkyl alternatively of 1～36 carbon atom,
R
2And R
3Can form together and comprise and R
2And R
3The ring of the nitrogen-atoms that connects, if desired, described ring is substituted, and/or comprises extra heteroatoms, and
R
2And R
3Be not hydrogen atom simultaneously,
It is characterized in that the following fact:
(III) is dissolved in the organic solvent with described amine, or is dissolved in the described diester compound (II),
When described amine (III) is dissolved in the organic solvent, described diester compound (II) is joined in the reaction mixture that comprises described amine (III) and described basic cpd,
When described amine (III) is dissolved in the described diester compound (II), described basic cpd is joined in the reaction mixture that comprises described amine (III) and described diester compound (II),
Described being reflected at more than or equal to carrying out under 30 ℃ the temperature,
Based on described diester compound (II), described amine (III) exists with the molar excess in 0.01～50% scope.
The method according to this invention, described amine (III) always is present in a kind of reaction medium that joins wherein in the compound (diester or basic cpd), and another kind of compound (basic cpd or diester compound) just exists with described amine from the reaction beginning.
Therefore, the diester compound of formula (II) participates in the method for the present invention, and this compound advantageously has following characteristics.
The favourable embodiment according to the present invention, in formula (I) with (II), A comprises 2～12 carbonatoms, the divalent alkyl of the side chain of preferred 3～6 carbonatoms.
Preferably, in formula (I) with (II), R
1Group is identical or different, is the alkyl that comprises 1～16 carbon atom, and can has one or more substituting groups.As example and unrestricted " substituting group " mean the alkyl that preferably has 1～4 carbon atom, preferably have alkoxyl group, hydroxyl or a halogen of 1～4 carbon atom.
Preferably, R
1Group is identical or different, is selected from alkyl, thiazolinyl, cycloalkyl, aryl and aralkyl, and described group can have one or more substituting groups.
More specifically, R
1Be preferably selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, isohexyl, Sec-Hexyl, cyclohexyl, methylcyclohexyl, the 2-ethyl-butyl, the 3-methyl amyl, n-heptyl, different heptyl, Zhong Gengji, 3-methyl hexyl, 4-methyl hexyl, the 1-ethyl pentyl group, the 2-ethyl pentyl group, the 3-ethyl pentyl group, n-octyl, iso-octyl, the 3-methylheptyl, n-nonyl, positive decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl.
In particularly advantageous embodiment, R
1Be selected from methyl and ethyl.
Most preferably, the diester compound of formula (II) is to have as above-mentioned defined R
1The mixture of following formula (II.1), (II.2) and diester compound (II.3):
R
1OOC-CH(CH
3)-CH
2-CH
2-COOR
1(II.1)
R
1OOC-CH(CH
2-CH
3)-CH
2-COOR
1(II.2)
R
1OOC-CH
2-CH
2-CH
2-CH
2-COOR
1(II.3)
The mixture of formula (II.1), (II.2) and diester compound (II.3) can have following composition:
75wt%～95wt%, the compound of the formula (II.1) of preferred 85wt%～95wt%,
3wt%～23wt%, the compound of the formula (II.2) of preferred 4wt%～14wt%,
0.1wt%～10wt%, the compound of the formula (II.3) of preferred 0.1wt%～3wt%,
More preferably, for the mixture of above-mentioned formula (II.1), (II.2) and diester compound (II.3), R
1Group is methyl.This mixture especially can for by Rhodia with trade(brand)name
Two ester mixtures that IRIS sells.
The favourable embodiment according to the present invention, diester compound (II) is introduced into as pure compound, does not namely put it in the solution of organic solvent.Yet, this diester compound (II) can be put into the solution of organic solvent.According to the preferred embodiment of the present invention, organic solvent is selected from volatile organic solvent, and especially pure and mild ether is preferably selected from methyl alcohol, ethanol, tetrahydrofuran (THF) (THF) and their mixture.More preferably, organic solvent is methyl alcohol.
The amine of formula (III) also participates in the method for the present invention, and described amine advantageously has following characteristics.
Preferably, in formula (I) with (III), radicals R
2And R
3Identical or different, be to have one or more substituent alkyl that comprise 1～16 carbon atom.As example and unrestricted " substituting group " mean the alkyl that preferably has 1～4 carbon atom, preferably have alkoxyl group, hydroxyl or a halogen of 1～4 carbon atom.
Preferably, radicals R
2And R
3Identical or different, be selected from alkyl, thiazolinyl, cycloalkyl, aryl and aromatic alkyl group, described group can have one or more substituting groups.
First embodiment of the invention, R
2And R
3Identical or different, be selected from methyl, ethyl, hydroxyethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, hexyl and cyclohexyl.Preferably, R
2And R
3Be selected from methyl, ethyl and hydroxyethyl.
Second embodiment of the invention, R
2And R
3Form the ring of 5 or 6 atoms that comprise the nitrogen-atoms that they connect together, an atom of described ring can be another kind of heteroatoms, such as Sauerstoffatom.Preferably, R
2And R
3Form the ring that is selected from morpholine, piperidines and piperazine together.
The amine solvent of formula (III) in organic solvent, or is dissolved in the described diester compound (II).
According to the preferred embodiment of the present invention, described organic solvent is selected from volatile organic solvent, and especially pure and mild ether is preferably selected from methyl alcohol, ethanol, tetrahydrofuran (THF) (THF), and their mixture.More preferably, described organic solvent is methyl alcohol.
The amine of formula (III) is with advantageously between 10%～100%, and preferably between 30%～80%, and more preferably the weight concentration in the organic solvent between 40%～60% exists.Situation when this amine (III) exists with 100% concentration is corresponding to the embodiment of this amine solvent in described diester compound (II) and when not having extra organic solvent.
Method of the present invention has been used basic cpd.
Preferably, described basic cpd is the alkoxide of alkali alcoholate or alkaline-earth metal, is preferably selected from sodium methylate, sodium ethylate or potassium ethylate, potassium tert.-butoxide.Described basic cpd also can be selected from carbonate, especially salt of wormwood or yellow soda ash; Perhaps be selected from the alkyl titanic acid ester, such as butyltitanate.Described basic cpd also can be the mixture of several above-claimed cpds.Preferably, described basic cpd is sodium methylate.
According to the present invention, described basic cpd can pure compound uses or uses with the solution that for example has in solvent, the especially organic solvent of the identical essence of methyl alcohol with previous definition.Usually, described basic cpd is with advantageously between 5%～80%, and between preferred 10%～50%, and more preferably the weight concentration in the organic solvent between 20%～30% is present in the solution of organic solvent.
According to the present invention, the amine of the diester compound of formula (II) and formula (III) reacts with the ratio of hereinafter definition in the presence of basic cpd.
According to feature of the present invention, with respect to described diester compound (II), amine (III) exists with the molar excess in 0.01%～50% scope.Preferably, with respect to described diester compound (II), this amine exists with the molar excess in 1%～30% scope, and more preferably exists with the molar excess in 5%～20% scope.The stoichiometry that is used for obtaining the carboxylic acid amide esters compound of formula (I) is that the diester compound of every mole of formula (II) is the amine of 1 mole of formula (III), " molar excess " means in this article: based on this stoichiometric quantity, method of the present invention comprises that the molar excess of amine is in 0.01%～50% scope.
With respect to diester, described basic cpd is with the volumetric molar concentration between 0.01%～20%, preferably preferably introduces with the volumetric molar concentration between 3%～10%.
According to another characteristic of the invention, be reflected at more than or equal to carrying out under 30 ℃ the temperature.Preferably, be reflected at more than or equal to carrying out under 50 ℃ the temperature.Advantageously, be reflected between 30～130 ℃, preferably between 40～90 ℃, even more preferably under the temperature between 45～65 ℃, carry out.Being used for the required calorie of this temperature of control provides by reaction self or by external device (ED), for example by heating or cooling.
Advantageously, be reflected at 1～10 bar absolute pressure, preferably in 1～5 bar absolute pressure, even more preferably under the pressure of 1～3 bar absolute pressure, carry out.
Preferably, be reflected under the anhydrous condition and carry out, be i.e. the water of the maximum 0.2wt% of tolerable, the preferred water of 0.05wt% at most.
According to preferred embodiment, be reflected under the inert conditions and carry out, for example by using rare gas element, especially nitrogen purges.
According to the present invention, joining (diester or alkalescence) compound in the reaction mixture that comprises amine (III) can be disposable, add continuously or in batches.
According to the present invention, when reaction finishes, obtain the carboxylic acid amide esters compound of formula (I).When reaction finished, reaction mixture did not need the carboxylic acid amide esters compound is carried out any purification process rambunctious, from diamide compound the carboxylic acid amide esters compound separation is come out.Can only remove the volatile compound such as unreacted amine and solvent, especially evaporation is removed, and for example removes by distillation under reduced pressure.Medium can be handled with traditional operation well known by persons skilled in the art alternatively, especially neutralizes, filtration and cleaning step to be to remove the salt that forms in the reaction process.Thereby the carboxylic acid amide esters compound of the formula that obtains (I) has high purity and can directly use in expection is used, for example as solvent, especially as the solvent in plant protection is used.
The method according to this invention can be continuous or discrete process.
The method according to this invention has lot of advantages.When in the presence of with respect to the amine (III) of two ester mixtures with molar excess, and under the temperature more than 30 ℃, be applied to meet the mixture of formula (II.1), (II.2) and diester compound (II.3), for example
During IRIS, the particularly advantageous of the method according to this invention.
At first, it has high selectivity to carboxylic acid amide esters, and namely the selectivity of carboxylic acid amide esters is greater than 90%, even greater than 95%.Unexpectedly, although amine is excessive and temperature of reaction more than or equal to 30 ℃, form the diamide less than 5%.With at a lower temperature and do not have the reacting phase ratio of excessive amine, react also very fast.And, do not observe tangible medium color, and the reaction mixture when reaction finishes not needing principal product is carried out any purification process rambunctious, this has simplified method significantly and has improved productivity.
Embodiment
The present invention of following examples example, but do not limit the present invention.
Embodiment
Embodiment 1 (comparison): dimethylamine (gas) joins
The mixing of IRIS/ sodium methylate
In the thing-T=20 ℃
With the sodium methoxide solution in the methyl alcohol (solution of 50wt%, weight 18.8g) and 304g by Rhodia with trade(brand)name
The mixture of 2-methyl-pentanedioic acid diester, 2-ethyl-succinic diester and di adipate that IRIS sells adds and is provided with mechanical stirring and in advance in the dry well-beaten 1 liter double jacket reactor of crossing.
See that reaction medium has safran.
The temperature-stable of this reaction mixture in set(ting)value+20 ℃, and is blasted dimethylamine gas two hours (adding the 82g dimethylamine, is 5% molar excess with respect to diester) in the reaction medium that comprises sodium methylate and two ester mixtures.
During whole blasting, it is constant that the temperature of reaction medium keeps.
The temperature of reaction medium remains on+and 20 ℃ up to the diester (deadline: 20 hours) that consumes 96% initial adding.
Under the temperature between 20 ℃～50 ℃, (about 200mbars) distillation under reduced pressure is excessive dimethylamine slightly.Come the neutralization reaction medium by 85% the phosphoric acid that adds q.s then.Filter formed salt.With the formed solid of washed with methanol, and volatile matter distillation compound (methyl alcohol and unreacted diester) under the vacuum then.
Then by the gc analysis product.
Following table 1 has been gathered condition and the result of this comparative example 1C.
Table 1
(a) finish the required time length of reaction
(b) in this case, the composition of when processing finishes, mentioning
(c) concentration ratio of the final diamide/carboxylic acid amide esters of Di/EA=
As can be seen, this sluggish, and the product that obtains has color.
Embodiment 2 sodium methylates join
In the IRIS/ dimethylamine mixture-Temperature Influence
Be provided with mechanical stirring and in advance in the dry well-beaten 1 liter double jacket reactor of crossing, with dimethylamine (pure DMA, 83g are 5% molar excess with respect to diester) introduce and be dissolved in 304g by Rhodia with trade(brand)name
In the mixture of 2-methylglutaric acid diester, 2-ethyl succinic diester and di adipate that IRIS sells.
In required set(ting)value (with reference to following table 2), and in for some time that limits, (solution of 50wt%, weight 18.8g) pours in the reaction mixture of the mixture that comprises dimethylamine and diester with the sodium methoxide solution in the methyl alcohol with the temperature-stable of reaction medium.
Pour in case finish, the temperature of reaction medium is kept constant, up to consuming the diester load that surpasses 96% adding.
Under the temperature between 20 ℃～50 ℃, under reduced pressure (about 200mbars) distills excessive dimethylamine.Come the neutralization reaction medium by 85% the phosphoric acid that adds q.s then.Filter formed salt.With the residual solid of washed with methanol, and volatile matter distillation compound under the vacuum then.
Then by the gc analysis product.
Following table 2 has been gathered two experiments implementing (experiment 2C: relatively; And test 2: according to the present invention) condition and result.
Table 2
(a) finish the required time length of reaction
(b) in this case, the composition of when processing finishes, mentioning
(c) concentration ratio of the final diamide/carboxylic acid amide esters of Di/EA=
As can be seen, the sluggish of comparative example 2C, and very fast according to embodiments of the invention 2 reactions, in embodiment 2, although temperature value rises to 50 ℃, but still keep selectivity.
Embodiment 3
IRIS joins in sodium methylate/dimethylamine mixture-Temperature Influence-mistake
The influence of amount DMA.
Dimethylamine in methyl alcohol (50wt% solution, weight 188g) and the sodium methylate in methyl alcohol (50wt% solution, weight 18.8g) introduced be provided with mechanical stirring and in advance in the dry well-beaten 1 liter double jacket reactor of crossing.
With the temperature-stable of reaction medium in required described value, and in for some time that limits, with 304g by Rhodia with trade(brand)name
The mixture of 2-methylglutaric acid diester, 2-ethyl succinic diester and di adipate that IRIS sells is poured in the reaction mixture that comprises dimethylamine and sodium methylate.
Pour in case finish, the temperature of reaction medium is kept constant, up to consuming the diester load that surpasses 96% adding.
Under the temperature between 20 ℃～50 ℃, under reduced pressure (about 200mbars) distills excessive dimethylamine.Come the neutralization reaction medium by 85% the phosphoric acid that adds q.s then.Filter formed salt.With the residual solid of washed with methanol, and volatile matter distillation compound under the vacuum then.
Then by the gc analysis product.
Following table 3 and table 4 have been gathered condition and the result of the different experiments of implementing (C is corresponding to comparative experiments).
Temperature Influence
The DMA of diester/DMA/ sodium methylate=1mol/1.2mol/0.05mol-50wt% in methyl alcohol.
Table 3
(a) finish the required time length of reaction
(b) in this case, the composition of when processing finishes, mentioning
(c) concentration ratio of the final diamide/carboxylic acid amide esters of Di/EA=
As can be seen, speed of reaction significantly reduces forward from 40 ℃, although kept the selectivity of esteramides.
The stoichiometric influence of DME
The DMA of diester/sodium methylate=1mol/0.05mol-50wt% in methyl alcohol.
Table 4
(a) finish the required time length of reaction
(b) in this case, the composition of when processing finishes, mentioning
(c) with respect to diester, the molar excess of DMA (mol%)
(d) concentration ratio of the final diamide/carboxylic acid amide esters of Di/EA=
As can be seen, do not have excessive DMA, react very slow.Under 50 ℃ of temperature, excessive DMA provides unusually and keeps optionally possibility of esteramides, these 50 ℃ of temperature further to promote the kinetics of reacting.
Claims (17)
1. method for the preparation of the carboxylic acid amide esters compound of following formula (I):
R
1OOC-A-CONR
2R
3(I)
Described method is included in the step that the amine of the diester compound that makes following formula (II) under the existence of basic cpd and following formula (III) reacts:
R
1OOC-A-COOR
1(II)
HNR
2R
3(III)
Wherein:
A is covalent linkage, or comprises the divalent alkyl of the straight or branched of 1～12 carbonatoms,
R
1Be the substituted alkyl alternatively that comprises 1～36 carbon atom,
R
2And R
3Identical or different, be to be selected from hydrogen and to comprise group in the substituted alkyl alternatively of 1～36 carbon atom,
R
2And R
3Can form together and comprise and R
2And R
3The ring of the nitrogen-atoms that connects, if desired, described ring is substituted, and/or comprises extra heteroatoms, and
R
2And R
3Be not hydrogen atom simultaneously,
It is characterized in that:
(III) is dissolved in the organic solvent with described amine, or is dissolved in the described diester compound (II),
When described amine (III) is dissolved in the organic solvent, described diester compound (II) is joined in the reaction mixture that comprises described amine (III) and described basic cpd,
When described amine (III) is dissolved in the described diester compound (II), described basic cpd is joined in the reaction mixture that comprises described amine (III) and described diester compound (II),
Described being reflected at more than or equal to carrying out under 30 ℃ the temperature,
Based on described diester compound (II), described amine (III) exists with the molar excess in 0.01～50% scope.
2. method according to claim 1, wherein, A comprises 2～12 carbonatoms, the divalent alkyl of the side chain of preferred 3～6 carbonatoms.
3. method according to claim 1 and 2, wherein, R
1Group is identical or different, for having one or more substituent alkyl that comprise 1～16 carbon atom.
4. according to each described method in the claim 1 to 3, wherein, R
1Group is identical or different, is selected from alkyl, thiazolinyl, cycloalkyl, aryl and aralkyl, and described group can have one or more substituting groups.
5. according to each described method in the claim 1 to 4, wherein, R
1Be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, sec-butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, isohexyl, Sec-Hexyl, cyclohexyl, methylcyclohexyl, the 2-ethyl-butyl, the 3-methyl amyl, n-heptyl, different heptyl, Zhong Gengji, 3-methyl hexyl, 4-methyl hexyl, the 1-ethyl pentyl group, the 2-ethyl pentyl group, the 3-ethyl pentyl group, n-octyl, iso-octyl, the 3-methylheptyl, n-nonyl, positive decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl.
6. according to each described method in the claim 1 to 5, wherein, the described diester compound of formula (II) is to have each defined R in the claim 1 to 5
1The mixture of following formula (II.1), (II.2) and diester compound (II.3):
R
1OOC-CH(CH
3)-CH
2-CH
2-COOR
1(II.1)
R
1OOC-CH(CH
2-CH
3)-CH
2-COOR
1(II.2)
R
1OOC-CH
2-CH
2-CH
2-CH
2-COOR
1(II.3)。
7. method according to claim 6, wherein, the mixture of formula (II.1), (II.2) and diester compound (II.3) has following composition:
75～95wt%, the compound of the formula of preferred 85～95wt% (II.1),
3～23wt%, the compound of the formula of preferred 4～14wt% (II.2),
0.1～10wt%, the compound of the formula of preferred 0.1～3wt% (II.3).
8. according to claim 6 or 7 described methods, wherein, R
1Group is methyl.
9. method according to claim 1, wherein, R
2Group and R
3Group is identical or different, is selected from alkyl, thiazolinyl, cycloalkyl, aryl and aralkyl, and described group can have one or more substituting groups.
10. method according to claim 9, wherein, R
2And R
3Identical or different, be selected from methyl, ethyl, hydroxyethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, hexyl and cyclohexyl.
11. method according to claim 1, wherein, R
2And R
3Form together and comprise and R
2And R
3The ring of 5 or 6 atoms of the nitrogen-atoms that connects, an atom of described ring can have another kind of heteroatoms, for example Sauerstoffatom.
12. method according to claim 11, wherein, R
2And R
3Form the ring that is selected from morpholine, piperidines and piperazine together.
13. according to each described method in the claim 1 to 12, wherein, with the described amine solvent of formula (III) in organic solvent.
14. method according to claim 13, wherein, described organic solvent is selected from pure and mild ether, is preferably selected from methyl alcohol, ethanol, tetrahydrofuran (THF) (THF) and their mixture.
15. according to each described method in the claim 1 to 14, wherein, described basic cpd is the alkoxide of alkali alcoholate or alkaline-earth metal, is preferably selected from sodium methylate, sodium ethylate or potassium ethylate, potassium tert.-butoxide, salt of wormwood or yellow soda ash, alkyl titanic acid ester and their mixture.
16. according to each described method in the claim 1 to 15, wherein, with 0.01～20%, preferred 3～10% volumetric molar concentration adds described basic cpd with respect to described diester compound.
17. according to each described method in the claim 1 to 16, wherein, described being reflected between 30 ℃～130 ℃ preferably between 40 ℃～90 ℃, and further preferably carried out under the temperature between 45 ℃～65 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1054534A FR2961205B1 (en) | 2010-06-09 | 2010-06-09 | PROCESS FOR THE PREPARATION OF ESTERAMIDE COMPOUNDS |
| FR1054534 | 2010-06-09 | ||
| PCT/FR2011/051315 WO2011154661A1 (en) | 2010-06-09 | 2011-06-09 | Process for preparing esteramide compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103201256A true CN103201256A (en) | 2013-07-10 |
| CN103201256B CN103201256B (en) | 2016-08-03 |
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ID=42751873
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180031774.5A Active CN103201256B (en) | 2010-06-09 | 2011-06-09 | For the method preparing carboxylic acid amide esters compound |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9284262B2 (en) |
| EP (1) | EP2580186B1 (en) |
| JP (1) | JP2013528200A (en) |
| CN (1) | CN103201256B (en) |
| BR (1) | BR112012031314A2 (en) |
| FR (1) | FR2961205B1 (en) |
| WO (1) | WO2011154661A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393886A (en) * | 2020-05-14 | 2020-07-10 | 黄山华惠科技有限公司 | Hydroxyalkyl amide curing agent and preparation method and application thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2957596B1 (en) * | 2010-03-18 | 2013-07-12 | Rhodia Operations | NOVEL ESTERAMIDE COMPOUNDS, PREPARATION METHODS AND USES THEREOF |
| FR2961206B1 (en) * | 2010-06-09 | 2012-07-20 | Rhodia Operations | PROCESS FOR THE PREPARATION OF ESTERAMIDE COMPOUNDS |
| EP2880068A1 (en) | 2012-08-06 | 2015-06-10 | Solvay Specialty Polymers Italy S.p.A. | Hybrid fluoropolymer composition |
| EP2935420B1 (en) | 2012-12-19 | 2018-05-16 | Solvay SA | Method for manufacturing sulfone polymer membrane |
| US10696768B2 (en) | 2014-02-28 | 2020-06-30 | Solvay Speciality Polymers Italy S.P.A. | Crosslinkable fluoropolymers |
| EP3140359A1 (en) | 2014-05-09 | 2017-03-15 | Solvay Specialty Polymers Italy S.p.A. | Fluoropolymer compositions |
| WO2015193321A1 (en) | 2014-06-19 | 2015-12-23 | Solvay Specialty Polymers Italy S.P.A. | Fluoropolymer composition |
| FR3041357B1 (en) * | 2015-09-17 | 2017-09-01 | Rhodia Operations | DETACHING SOLVENTS OF PHOTOSENSITIVE RESINS |
| EP3389877B1 (en) | 2015-12-16 | 2023-04-26 | Solvay Specialty Polymers Italy S.p.A. | Multilayer assembly |
| WO2019096800A1 (en) | 2017-11-14 | 2019-05-23 | Solvay Specialty Polymers Italy S.P.A. | Multilayer assembly |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3417114A (en) * | 1965-07-20 | 1968-12-17 | C P Hall Company Of Illinois | Method of making amides from moisture and acid-gas containing esters |
| CN101098851A (en) * | 2005-01-13 | 2008-01-02 | 出光兴产株式会社 | Beta-alkoxypropionamides, solvents, detergents and liquid pharmaceutical compositions and process for preparing beta-alkoxypropionamides |
| WO2009092795A1 (en) * | 2008-01-25 | 2009-07-30 | Rhodia Operations | Use of ester amides as solvents, ester amides as such, and method for preparing ester amides |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288794A (en) | 1962-09-12 | 1966-11-29 | C P Hall Company Of Illinois | Method of making amides of dimethylamine and piperazine |
| EP0143303A3 (en) | 1983-10-29 | 1986-04-30 | Bayer Ag | Process for the preparation of substituted succinic-acid amides |
| EP0445096A1 (en) * | 1990-02-26 | 1991-09-04 | Monsanto Company | Process for preparing metal-free fatty peroxyacid precusors having amide moieties in the fatty chain |
| US5325093A (en) * | 1991-05-08 | 1994-06-28 | Sony Corporation | Analog-to-digital converter for composite video signals |
| US5166407A (en) * | 1992-01-27 | 1992-11-24 | Monsanto Company | Process for preparing fatty peroxyacid precursors having amide moieties in the fatty chain |
| FR2961206B1 (en) * | 2010-06-09 | 2012-07-20 | Rhodia Operations | PROCESS FOR THE PREPARATION OF ESTERAMIDE COMPOUNDS |
-
2010
- 2010-06-09 FR FR1054534A patent/FR2961205B1/en not_active Expired - Fee Related
-
2011
- 2011-06-09 JP JP2013513736A patent/JP2013528200A/en not_active Ceased
- 2011-06-09 CN CN201180031774.5A patent/CN103201256B/en active Active
- 2011-06-09 EP EP11734161.0A patent/EP2580186B1/en active Active
- 2011-06-09 WO PCT/FR2011/051315 patent/WO2011154661A1/en active Application Filing
- 2011-06-09 US US13/702,470 patent/US9284262B2/en active Active
- 2011-06-09 BR BR112012031314A patent/BR112012031314A2/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3417114A (en) * | 1965-07-20 | 1968-12-17 | C P Hall Company Of Illinois | Method of making amides from moisture and acid-gas containing esters |
| CN101098851A (en) * | 2005-01-13 | 2008-01-02 | 出光兴产株式会社 | Beta-alkoxypropionamides, solvents, detergents and liquid pharmaceutical compositions and process for preparing beta-alkoxypropionamides |
| WO2009092795A1 (en) * | 2008-01-25 | 2009-07-30 | Rhodia Operations | Use of ester amides as solvents, ester amides as such, and method for preparing ester amides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393886A (en) * | 2020-05-14 | 2020-07-10 | 黄山华惠科技有限公司 | Hydroxyalkyl amide curing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2961205B1 (en) | 2012-06-29 |
| WO2011154661A1 (en) | 2011-12-15 |
| US9284262B2 (en) | 2016-03-15 |
| US20130237722A1 (en) | 2013-09-12 |
| EP2580186B1 (en) | 2017-08-16 |
| FR2961205A1 (en) | 2011-12-16 |
| JP2013528200A (en) | 2013-07-08 |
| EP2580186A1 (en) | 2013-04-17 |
| CN103201256B (en) | 2016-08-03 |
| BR112012031314A2 (en) | 2016-10-25 |
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